Sealing compounds



Patented Dec. 21, 1948 s PATENT OFFICE SEALING COMPOUNDS John D. Morgan, South Orange, and Russell E. Lowe, East Orange, N. J., assignors to Cities Service Oil Company, New York, N. Y., a corporation of Pennsylvania No Drawing. Application March 30, 1945, Serial No. 585,822

14 Claims.

. 1 1 This invention relates to improved sealing compounds, for use in forming tight joints in gas and vapor lines; between cylinder heads and their associated cylinder blocks; and in other places Where mechanical joints must have their abutting faces treated with plastic material to render them leak-proof.

Conventional sealing compounds of the kinds employed in unions, pipe couplings, and the like, are of such a character that they set up into hard, cement-like coatings within a relatively short time after the matching faces of the coupling devices have been drawn tightly together. This action does not necessarily reduce the effectiveness of the compound as a sealing agent, although this has sometimes happened. It does produce a seizing of the joined surfaces which is difilcult to break when repairs become necessary, and it frequently results in a galling and scoring of the coupling surfaces when they are forcibly broken apart. It is common experience, for example, upon opening a union which has been sealed for a comparatively short time, to find that its faces are so badly pitted and scored as to require the use of new coupling parts in a replacement of the joint. In those cases in which such compounds are applied to the surfaces of gaskets which in turn are interposed between the faces of the joints, the setting up of the sealing paste usually makes it necessary to destroy the gasket in the course of breaking the joint. Even where the gasket can be removed without material injury it will be found to be so stiff and hard as a result of the setting up of the compound as to render it unfit for reuse. This means, of course, that new gaskets must be employed each time a joint of this kind is reformed, with attendant trouble and expense.

' The admixing of a petrolatum or soap greases with sealing compounds has the effect of lengthening the time within which they remain in plastic condition and tends to offset to some extent the objections heretofore outlined. The improvement is, however, of a rather transitory nature for even these softened compounds will set up in the course of events. It is also apparent that the use of these softened agents very greatly limits the utility of the resulting compounds. It is quite obvious, for example, that a compound contain ing petroleum jelly has little or no utility in sealing "a gasoline line, for it will soon be washed away by'the solvent action of the gasoline and allow leaks to develop. Similarly, soap softened compoundsfiare not of much value in sealing compounds which are subject to the solvent acability to chemical change, particularly at elevated temperature-s, and to the fact that their consistencies vary over an extremely wide range with changing temperatures, wherefore the sealing compound may be too soft to be retained in the joint under some conditions or too hard to be applied to it under others. 7

All of the foregoing problems of establishing and maintaining leak tight joints with existing compounds become peculiarly acute in aircraft work where lines for the transmission of gasoline, hydraulic fluids, and high pressure oxygen izo mention but a few-must be maintained absolutely leak tight for reasons of safety as well as economy. It will be recognized that these fluid lines are a favorite target for enemy gunfire in combat, as well as being subject to continuous and excessive vibration in the most peaceful ofoperations. The joints must therefore be opened to allow for replacement or inspection perhaps more frequently in this than in any other kind of service. A further complication of course arises from the fact that aircraft fluid lines are subject to rapid and extreme changes of temperature which tend to open up their joints unless the sealing compound employed retains a'plastic'character so that it will always accommodate itself to changing conditions. a The principalobject of the invention is top rovide a-soft, jelly-like composition of matter which retains a-substantially uniform lasticity for extended periods of time, far beyond anything heretofore known in the Way of sealing com-; pounds, and which is neither affected by excessive heat nor by the solvents of normal gases and liq z uids, whereforeit is particularly well suitedas-a base for compounds. which areemployed in the terial, arenot soluble in water, gasoline, naphtha, or any of the ordinarily used commercial solvents,

sealing of mechanical joints.

It is a further object of the invention to pro;

joint, which adheres well to such surfaces, and

isneither subject to oxidation, polymerization or other chemical change even after'l'o'ng continued heating in the presence of oxygen and otherg'ases.

at extremely high temperatures and pressures. i'

Another object of the invention is to provide a sealing paste of the foregoin character in which the components, and particularly the base mawhich is neither flammable nor capable of sustaining combustion, and which appears to have no corrosive effect upon copper, steel, aluminum, and the other ordinary materials of construction.

We have discovered that a substantially fully polymerized thermo -setting plastic tsuchras the reactionlproduct of phenol formaldehyde con densation can be dispersed in a synthetic oily liquid to form a soft, jelly-like composition, the consistency of which may be varied inthe formation of the gel to suit individual requirements, and which, once established, will-Joe retainedijor indefinitely long periods of time even whenithe gel is subjected to extremely high temperatureszand pressures. In formin the gel we have found that tri-o-cresyl phosphate, tri-octyl phosphate.

and di-butyl phthalate are well adapted to act as the liquid phase in which the phenolic resin is dispersed, and that the resulting products are chemically inert, being subject to neither oxidationnnolymerizat on, s t-her chemical chan e whieh ,-w.0 1 vary thei e sent al prope ti s. n addition, w rfind :tha :these pre incts a so uble in any of the commerc a ali h t or aromat s vents- W ave urt disc r d hat ta e and :eraphi-te th he work nto the fore oin eel mfcr v as s of va y n e si teneie whi hretain a-his -degre ,o las for incredibly long periods .of time and which, becauseof their inert character, are ideally suited for use as joint sealing compounds. In compoundin -these sealing pastes we prefer to employ frornfifi to 'ZOpercent by weightofthe gel; from i 0 ,to,29-pe r cent of;talc-- which serves primarily asa fillerfiand small quantities'of graphite varying-betweensay 5 and 1 per centofthe weight of thetotalcpmposition to farm products of varying consistency, which have proven highly effective inthe sealing of joints .in .high pressure oxygen lines; in gasoline and oil piping systemsand in a wide ietyiof.other-mechanical joints which are suhject to high temperature, high pressure, or Q th asw-ell as .to theactionof liguidsand gases ofla highlysolvent nature.

iQheexe p ee a omp un n acc n e t the invention has the followin formula in which e e ee tae sa eeiven.by iehtwith es tethezto alcompos t o Percent Gel of phenol formaldehyde coh lensationand Inpreparing the gel for the example composition-we-mixed about 17 per cent by weight of an clouding at 'atemperature of about 415 E, which became increasingly evident until the liquid reached a state of complete opacity ata t e1 n ne atu epia eu 45 F. Th e act e pe tu e at which clouding would first benoted cannot he ta ed with pr is on b use .it has been found to va y ven in t e e a at on of el f m th samereaction products, and .to someextent'upon t e amo nt of solven m yed for the resin- We have found, however, that when the temperature raised .from 20 .to ,30above the point ,of first hazin a reactionoccurs in which the,en-,-

4- tire mass goes over suddenly from liquid state to a thick and heavy gel. It may also be noted-that during the heating operation, and particularly after the driving off of the alcohol and acetone 5 solvents for the resin, there was a heavy evolution ,of dorm-aldehyde yapor hich stqpped jigst about as u de i tth ie linstreaetiphstarted. At that point, namely when the jelling reaction was isstarted, we immediately discontinued both the 10 heatingand stirring and allowed the gel to cool to room temperature.

Thecharacter o flthe phenol formaldehyde resin .whiohais employedappears to be highly critical to zthefformationlof asuitable gel. We have found, forexamp'le that-the starting product must not have beencarried much beyond first stage poly merization and that it should contain an excess of formaldehyde.

I-he gel of the foregoing resin solution and trio-cresyl phosphate was-.a stifi, jelly-like product having: a clear,.:ruddy brown color andwhiclngave evidence 0f being a colloidal dispersionof iully polymerized resin rather than .a true xcompoun'd of rthe resinland phosphate. Thus,:when the -gel wassubjected-to'long continued heatingat a temperature of fI'Om..-.'5fi0 to 1600" the trieo cresyl phosphate was evaporated away, leavinga mass ofrfully polymerized phenolic condensation-product. wViEhether: this :is .so :or ,not, '.we shall :refento theigel .as acolloida-l dispersion of afullyzpolym-em ized resin 'for .easy description. This vprodu'ct as such, was F1300 stilt and rubber-like incharacter -to spreadeasi-lyein, arequirement of a seali-ngmom poundH-and rweraccordingly worked it--"in a -"col loid= millsuntili it was reduced -to I a=unit0rmly plastic.-;product.:having the general consistency o'f-=a cupL-g-rease. iI o this. we added small quantities of .italc'tandgraphite referred to above :and kneadedthem 1 in until a homogeneous paste-was obtained,- which was -then ready forhse-a's a seal ingi roduct. y

1In testing the -sealing properties iof the paste, Werjoined together a number of short lengths 0f gtinohgbrass pipe :with standard 'brass' fittings, the threaded portions :of each joint lbeing thor- OUghIMCOatGd'LWith the exampletpaste before-final assembly tosform a ;line .which wasiclosedgat one end. ,Thataline then :c'onnecte'd'to ran OXYH gen tanlvand {subjected -sto-.;,a 1pressuretof x2150 lies. per :sq in, after which itjiWfiSilhfifitfidfitOgfi. temperature .;of @about 575? and ,held there f a -.pe.riod-.of about 50 minutes. 'when-zthezline had hee ed .zsuiiieient y. We s mm rse l iit 1m. iW' r.

hi sstili containin .oxyeentat thezhi hinnese sure iustimehti neiifor :thepurnese ofi-detectm e k -Which m ht have devel ped n the sealed point :A caref tins-n eti n out and merged line failed to disclose the form n' ofi thubble around thei int endear-e eve e iden e that the connectie :hael. beehsmaine a ned lsnseal dth eueheutt etest: wh msyeeh p ly wa :th n shutiofi and each 2 he joints was broken-for inspection. .It My noted that theio nts. cam apart very .rea it, th r being no ev d nc -o sei n z and .inspeev t en sho ed tha their fac s ahdthreaded mere t onsswere .fr .ir m eall h and-vron h, that the coatingsof sealing teornpds it gn; lu t. ab u so t neopla ic as at he time-ht application. Further tests have demonstrated ha th eempos t on a s its-plasti,

we have benun'able to discover any tendency .an

75. l ephlg .ot ire-materialize set was aaltesll ttqf the application of high temperatures and pressures.

In a separation test such as that to which soap greases are frequently subjected we held the example composition at a temperature of 450 F. for a period of 24 hours. At the end of that time there was no evidence of separation of the talc and graphite from the gel, or of the resin from the tri-o-cresyl phosphate-that is to say, there had been no reaction comparable to the bleeding of the grease. It was evident, however, that some very slight amount of tri-o-cresyl phosphate had been evaporated away. The sealing compoundwaahowever, still soft and pliable, even with the loss of some of its phosphate content and was still entirely suitable for use as a sealing compound. The sealing compound was additionally tested for solubility and for chemical activity. It proved to be completely insoluble in water at 212 F., in boiling benzenes, toluene, and other aromatic solvents, as Well as in aliphatic diluents such as methyl and ethyl alcohol, ethyl ether, chloroform and the like, and Was wholly unaffected by tri-butyl phosphate, and other commercial solvents. Insofar as chemical activity is concerned, we have been unable to find any evidence of oxidation product when subjected to the pressure of oxygen at 2150 lbs. per sq. in. and at 575 F., and have demonstrated that the sealing compound will not support combustion. Standard corrosion tests show that it has no effect upon copper, brass, aluminum or steel, or the various alloys of these materials.

The consistency of the gel which is employed as a base may be varied within wide limits in the course of its preparation by the variation of suitable percentages of resin solution and trio-cresyl phosphate. We have, for example, prepared gels ranging in consistency from that of a thick, heavy oil at one end of the scale to a product having about the consistency of a hard cup grease by the use of from 5 to 20 per cent of phenolic resin solution, and from 95 to 80 per cent of tri-o-cresyl phosphate. It should be noted, however, that the final consistency of the product is determined in the course of its preparation and that once the gel has been formed, it cannot be made softer by the addition of trio-cresyl phosphate, or harder by adding phenolic resin solution, for neither of these products is soluble in, or compatible with, a completed gel.

We have found that We can also prepare gels of the phenolic resin solution described above with tri octyl phosphate, and with di butyl phthalate, the procedures for preparing them being substantially the same as that described above for the formation of tri-o-cresyl phosphate gel, and that these gels can also be blended with talc and graphite fillers to form excellent sealing compounds. The ratios of fillers to the tri octyl and di butyl phthalates may be substantially the same as those given for the tri-o-cresyl gel; and the consistency of these gels may be varied in their formation by the use of from 5 to 20 per cent of the resin solution with 95 to 80 per cent of the liquid phase material.

The new gel compositions are claimed in a separate application Serial No. 585,823, filed.

March 30, 1945, now abandoned, and our present application is confined to claims to sealing compositions of the gels with suitable fillers.

Having described our invention, what we claim as new is:

1. A compound for sealing mechanical joints comprising a major proportion of a gel of a substantially fully. polymerized, thermosetting; phenol-formaldehyde resin dispersed in tri-ocresyl phosphate, said gel having about the consistency of a soft cup grease, and minor proportions of talc and graphite, uniformly distributed through said gel to form a paste.

2. A' compound for sealing mechanical joints and the like comprising from about 55 to about '70 per cent by weight of a gel of a substantially fully polymerized, thermosetting, phenol-formaldehyde resin dispersed in tri-o-cresyl phosphate, from about 40 to about 29 per cent by weight of talc and from about 5 to about 1 per cent'by weight of graphite, said talc and graphite being uniformly distributed through said gel.

3. A compound for sealing mechanical joints comprising about 65 per cent by weight of age! of a substantially infusible phenol-formaldehyde resin dispersed in tri-o-cresyl phosphate and having about the consistency of a soft cup grease, about 33 per cent by weight of talc, and about 2 per cent by weight of graphite. i

4. Acompound for sealing mechanical joints and the like comprising from about 55 to about '70 per cent by weight of a gel of a substantially fully polymerized, therm-osetting, phenol-formaldehyde resin dispersed in tri octyl phosphate, from about 40 to about 29 per cent by weight of talc and from about 5 to about 1 per cent by weight of graphite.

5. A compound for sealing mechanical joints and the like comprising from about 55 to about '70 per cent by weight of a gel of a substantially fully polymerized, therm'osetting, phenol-form aldehyde resin dispersed in di butyl phthalate, from about 40 to about 29 per cent by weight of talc and from about 5 to about 1 per cent by weight of graphite.

6. A compound for sealing mechanical joints comprising a gel of from about 4 to 16 per cent of a substantially fully polymerized, thermosetting, reaction product of phenol-formaldehyde condensation dispersed in from about 96 to 83 /3 per cent of an oily liquid of low vapor pressure chosen from the group consisting of tri-o-cresyl phosphate, tri-octyl phosphate, and di-butyl phthalate; and a filler uniformly mixed with said gel.

'7. A compound for sealing mechanical joints and the like comprising from about 4 to 16% per cent of a gel of substantially fully polymerized, thermo-setting, phenol-formaldehyde condensation product, and from about 96 to 83 per cent of tri-o-cresyl phosphate, as a base sealing mate rial; and a filler uniformly mixed with said gel 8. A compound for sealing mechanical joints and the like comprising a gel of from 12 to 16 /3 per cent by weight of a substantially fully polymerized, thermo-setting, phenol-formaldehyde condensation product dispersed in from 88 to 83 per cent by weight of tri-o-cresyl phosphate, said gel constituting the base sealing ingredient; and a filler.

9. A compound for sealing mechanical joints and the like comprising a gel of about 14 per cent by weight of a substantially fully polymerized, thermosetting, phenol-formaldehyde con densation product dispersed in about 86 per cent by weight of tri-o-cresyl phosphate, said gel con stituting the base sealing material; and a filler uniformly mixed with said gel.

10. A compound for sealing mechanical joints comprising a gel of from 4 to 16 per cent of a substantially fully polymerized, thermosetting, 

